Production of oil soluble azo coloring matters



Patented Jan. 17, 1928.

UNITED STATES PATENT OFFICE.

JAMES P. PENNY OF BUFFALO, NEW YORK, ASSIGNOR TO NATIONAL ANILINE & CHEMICAL (70., INQ, OF NEW YORK, N. Y., A CORPORATION OF NEW YORK.

PRODUCTION OF OIL SOLUBLE AZO COLORING MATTERS.

No Drawing.

This invention relates to the manufacture and production of new azo coloring matters which are of value for coloring hydrocarbons, oils, fats, waxes, varnishes, etc. They are also of value as pigments. The material colored by the new azo coloring matters also constitutes a part of the present invention.

It is well known that the coloring matters produced by coupling a diazotized aromatic amino body, such as aniline or 'aminoazobenzene, or a homologue thereof, etc., into a phenol or a naphthol are generally more or less soluble in alcohol, hydrocarbons, oils, fats, waxes, etc.,- and are employed to a lesser or greater extent for coloring the same. Their usefulness, however, as coloring matters for said substances is large] a function of their solubility in them or 0 their capability of roducing highly dispersed or colloidal so utions oradmixtures therewith.

As pre ared by heretofore known processes,

they 0 ten contain an undesirable amount of matter insoluble in said substances or they lack the desired degree of solubility in them.

According to the present invention, in the production of azo coloring matters by coupling diazo compounds of the a lamines or of the aminoazo derivatives of t e aromatic hydrocarbons, more particularly aniline, its homologues, and alkoxy derivatives (i. e., OCH OC,H,, OC,H,, OOH,O,H,, etc.), which are free from an acid group, e. a carboxyl or a sulfo group, with a pheno l or a naphthol body, more especiall alphaand beta-naphthol, there is employe an excess of the diazo compound over and above that required for the production of a definite azo compound, and the excess of diazo compound is subsequentl decomposed preferably in the presence of t e resulting azo body and the composite colori'n matter then isolated and dried in any suitaile manner.

By incorporating the hydrolytic decomposition products of a diazo compound with the azo body, the coloring matters thus produced are more soluble in alcohol, hydrocarbons, oils, fats, waxes, etc., or are capable of giving superior colloidal or dispersed solutions or admixtures therewith, than the analogous products similarly produced but which are substantially free from the hydrolytic decomposition products of diazo bodies.

Application filed March 2, 1926. Serial No. 91,813.

The decomposition products of other and diil'erent diazo compounds, or a mixture of diazo com ounds, may also be employed in place of t ose arising from the particular diazo component or components used in the production of the azobody. That is, when the coupling between any given diazo compound and the phenol or naphthol body is completed in any suitable or well known manner for the production of an azo dyestufi, another and different diazo compound may be added under conditions whereby it is decomposed and prevented, or substantially so, from any coup ing action on its part.

In carrying out the process of the present invention, the diazo com ound is coupled with the phenol or napht ol component in any well-known or suitable manner. In case the phenol or naphthol body is being coupled with the maximum number of molecuhir proportions (i. e., moles) of the diazo component with which it is capable of coupling an excess of the diazo component may be present or it may be added at the completion of the combination, and said excess be decomposed, preferably after completion of the combination, in any suitable manner, for example, by means of heat or by standing over a considerable period of time, said decomposition being eifected preferably in the resence of water. \Vhere the phenol or naphthol body is being coupled into a definite, number of molecular proportions (moles) of the diazo component less than the maximum number with which it is capable of combining, the excess of diazo component is preferably added to the completed coupling at a sufliciently high temperature to rapidly decompose the diazo body and thus prevent or minimize it from coupling with the azo body present. It may be pointed out that the coupling of the diazo component with the phenol or naphthol component is usually carried out in alkaline media and such solutions particularly when strongly caustic in their reaction tend to promote the decomposition of diazo compounds, especially at elevated temperatures or upon standing at ordinary temperatures over a period of time.

The following specific examples will further illustrate the invention, but it will be Ill understood that the invention is not limited thereto. The parts are by Weight.

Example 1.-A solution of 18 parts (1.94 moles) of aniline in 60 parts of water, 50 parts of 20 B hydrochloric acid and suflicicnt ice (about 80 parts) to bring and maintain the solution at a temperature of about to 22 C. is diazotized in the usual manner by the addition of about 14.5 parts of sodium nitrite (96% purity). The iced solution thus obtained is then added I'apidlv to a Well-stirred solution of 8.5 parts (3.59 moles) of alpha-naphthol dissolved in 220 parts of water and 22.5 parts (5.6 moles) of caustic soda, the temperature being maintained at about 0 to 8 C. by the addition of suflicient ice (about 80 parts). The mixture is stirred for about an hour at 0 to 8 C. in order to complete the formation and precipitation of di(phenylazo)-alphanaphthol, and then for 1G to-18 hours without additional cooling. The temperature gradually rises to about C. and the mixture foams considerably due to the decomposi tion of the excess diazobenzene. It is then gradually heated to about 85 C. and the precipitated coloring matter filtered off, Washed well with warm (about (3.) water and then with cold Water, dried at SO-85 C. and ground.

The coloring matter thus obtained is probably comprised of 2.4-di(phenylazo)-alpha-- naphthol, which corresponds with the prob able formula in admixture or combination with the hydrolytic decomposition products of diazobenzene, and in the dry state, is a dark brown powder, insoluble in water or in 10 percent caustic soda solution, sparingly soluble in alcohol giving a light brown solution, soluble in benzene giving a dark brown solution, and soluble in concentrated sulfuric acid with a dark to black solution which on dilution with Water gives a brown precipitate. It colors or stains wood, waxes, oils, fatty acids, benzene, etc., brown shades.

In the above example, there is employed an amount of diozobenzcne about percent in excess of that required to form di(phcnylazo) -alplm-naphtliol. The hydrolytic decomposition of this excess diazobenzcne (i. e., a decomposition eliectcd in the presence of water), and the incorporation of the decomposition products in combination, solution or admixture with di(phcnylazo)alpha-naphthol produces a product which is considerably more soluble in alcohol or in benzene than pure di (phenylazo) -alpha-naphthol. In

an analogous manner, in lace of aniline there may be employed ot er amines, for

ilarly prepared from thedihydroxy derivatires of the aromatic hydrocarbon, for ex ample, resorcin.

Example 2.l5.7 parts (1.15 moles) of crcsidine (i. e., 4-methyl-2-amino-l-mcthoxybenzene) dissolved in 400 parts water and 28 parts of 20 B hydrochloric acid are diazotized in the usual manner by means of about 7 parts of sodium nitrite, sufiicient ice being added to keep the temperature at about 0 to l-L-l parts (1 mole) of bctaaiaphthol are dissolved in 300 arts of Water con taining 10 parts of caustic soda, and cooled to about 0 (J. by the addition of ice. The diazotized cresiduie solution is added to the Well stirred beta-naphthol solution, the temperature being maintained at about 0 to 5 (1., by the addition of ice or by other suitable means. After stiring the mixture for about an hour in order to complete the formation and precipitation of the monazo dye, the solution is slowly heated to about -8tl O, to decompose the excess diazo solution and the coloring matter then filtered oil, washed well with Water, dried at about 60-S0 C. and ground to a powder.

The dyestuil thus obtained is probably comprised of 1-(2'-methoxy-5'-methylbenzene-lazo)-beta-naphthoi of the probable formula in admixture or combination with decomposition products of diazotized 4-methyl-2 auiino-lancthoxybenzcne. and is a red powder substantially insoluble in Water and in dilute caustic soda solution. It is soluble in alcohol or benzene to give a red solution,

llu

example, the product is filtered off before heating the solution to decompose the excess diazo body, l-(2' methoxy-5'-methylbenzene-1-azo)-beta-naphthol is obtained in a substantially pure condition and is considerably less soluble in benzene than when it- L'Ollllllilh' the decomposition products of diazo compounds. The substantially pure product may be employed in the manufacture of valuable lakes and pigments.

It will he llI1(lLl. l'O0\.l that the decomposition products derived from diazo compounds which are or may be present in the coloring matters contemplated by the present invention may vary in amount over a wide range without departing from the spirit and scope of the invention. It will be also understood that the term hydrolytic decomposition products as used in the present invention refers to and includes those products obtained by the decomposition of diazo bodies preferably in the presence of 2.20 bodies and alkaline aqueous media. They are of unknown composition, being complex mixtures, and are usually, though not always, tarry and resinous in nature.

In the claims it will be understood that the term phenol body denotes and includes, unless otherwise specilied, a hydroxy derivative of a benzene hydrocarbon and of naphthalene free from other substituents; that the term naphthol body denotes and includes alphaand beta-naphthol; and that the term arylamino body denotes and inz eludes, unless otherwise specified, amino and aminoazo compounds of the benzene and naphthalene series which are free from acid groups but may contain alkoxy groups.

I claim 1. In the production of an azo coloring matter soluble in benzene, a process which comprises incorporating the hydrolytic decomposition products of a diazotized arylamino body with an azo body derivable from a diazotized arylamino body and a phenol body.

2. In the production of an azo coloring matter soluble in benzene, a process which comprises incorporating the hydrolytic decomposition products of a diazotized arylamino body with an azo body derivable from a diazotized arylamino body of the benzene series and a naphthol body.

3. In the production of an azo coloring matter, a process which comprises incorporating the hydrolytic decomposition prodnets of a diazotized arylamino body of the benzene series with a commixture of azo bodies derivable from a diazotized aryl amino body and alphaand bcla-naphthol.

4. In the production oi an azo coloring matter soluble in benzene, a process which comprises incorporating hydrolytic decomposition products of a diuzotizcd aryl amino body of the benzene series with an azo body in presence ofthe azo body, and isolat in the composite product thereby produced.

6. A process of making an azo coloring matter soluble in benzene which comprises treating an azo body derivable from a diazotizecl arylamino body and a phenol body with a diazotized arylaminobody in the presence of water and alkali at a temperature at which the di'azo body is decomposed, and subsequently isolating the composite product thereby produced.

7. As a new product, a composition of matter comprising an azo body, derivable from a diazotized aryhunino body and a phenol body, in corporation with hydrolytic decomposition products of a diazotized arylamino body; said product being insoluble in water and soluble in benzene.

8. As a new product, a composition of matter comprising an azobody, derivable from a diazotized arylamino body of the benzene series and a naphthol, in oommixture with hydrolytic decomposition products of a. diazotized arylamino body of the benzene series; said product being insoluble in water and soluble in benzene.

9. As a new product, a composition of matter com rising azo bodies, drivable from a diazotizecl arylamino body of the benzene series and al haand beta-nah thol, in corporation with hydrolytic diacomposition products of a diazotized arylamino body.

10. As a. new product, a composition of matter comprising an azo body, derivable from a diazotized arylamino body of the benzene seriesv which contains an alkoxy group, and a naphthol, in corporation with decomposition products of a diazotized arylamino body; said product being insoluble in water and soluble in benzene.

11. As a new product, a composition of matter comprising a monazo dyestull' which corresponds with the following probable formula OR OH where R represents CH,,C H,,,C H,,C,H,, CH C H etc., in commixture with the hydrolytic decomposition products of a diazotized arylamino body.

12. As a new product, a composition of matter comprising an azo dyestufl' which in corporation with the hydrolytic decomposition products of diazotizcd 4-methyl-2- amino-l-methox'y benzene.

13. Material colored with the product of claim 7.

14. Material colored with the product of claim 8. I

15. Material colored with the product of claim 9.

16. Material colored with the product of 20 claim 10.

17. Material colored with the product of claim 11.

18. Material colored with the product of claim 12. i 25 i 19. In the production of an oil soluble az coloring matter, a process which comprises reacting a phenyl body with a diazotized arylamino body to form an azo body, and

subsequently decomposing a diuzotized arylamino body in presence of water and of said azo body.

- In testimony whereof I aflix my signature.

JAMES P. PENNY.

matter comprising an 120 dyestufi' which corresponds with the following probable formula:

OCH; JOH

in corporation with the hydrolytic decomposition products of diazotizt-d l-niel'liyl-ziamino-l-methoiy benzene.

13. hluterizil colored with the product of claim 7.

14. Material colored with the product of claim 8.

product of CERTIFICATE OF CORRECTION.

Patent No. l,656, 233.

Granted January 17, 1928, to

JAMES P. PENNY.

it is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 3, line 103, claim 9, for the misspelled word "drivable" read "derivable"; page 4, "line 28, claim 19, for the word "phenyl" read "phenol"; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 20th day of March, A. D. 1928.

Seal.

M. J. Moore, Acting Commissioner of Patents.

CERTlFICATE 0F CORRECTION.

Patent No. 1,656,233. Granted January 17, 1928, to

JAMES P. PENNY.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 3, line 103, claim 9, for the misspelled word "drivable" read "derivable"; page 4, line 28, claim 19, for the word "phenyl" read "phenol"; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 20th day of March, A. D. 1928.

M. J. Moore,

Seal. Acting Commissioner of Patents. 

